EP3443021B1 - Polyisoindolinonzusammensetzungen, verfahren zur herstellung und daraus geformte zusammensetzungen und artikel - Google Patents

Polyisoindolinonzusammensetzungen, verfahren zur herstellung und daraus geformte zusammensetzungen und artikel Download PDF

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EP3443021B1
EP3443021B1 EP17720652.1A EP17720652A EP3443021B1 EP 3443021 B1 EP3443021 B1 EP 3443021B1 EP 17720652 A EP17720652 A EP 17720652A EP 3443021 B1 EP3443021 B1 EP 3443021B1
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polyisoindolinone
independently
alkyl
same
different
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EP3443021A1 (de
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Dadasaheb V. PATIL
Prakash Sista
Robert Russell Gallucci
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SABIC Global Technologies BV
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
    • C08G65/4031—(I) or (II) containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
    • C08G65/4031—(I) or (II) containing nitrogen
    • C08G65/4037—(I) or (II) containing nitrogen in ring structure, e.g. pyridine group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
    • C08G65/4043—(I) or (II) containing oxygen other than as phenol or carbonyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
    • C08G65/4043—(I) or (II) containing oxygen other than as phenol or carbonyl group
    • C08G65/405—(I) or (II) containing oxygen other than as phenol or carbonyl group in ring structure, e.g. phenolphtalein
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
    • C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK

Definitions

  • compositions such as poly(isoindolinone ether ether ketone) compositions, their methods of manufacture, and articles comprising the composition.
  • Polyaryl ether ketones are a family of polymers containing aromatic ether units and ketone units.
  • An example is poly(ether ether ketone) (PEEK), which is known for a high melting point (greater than 330° C), excellent chemical resistance, thermal stability, hydrostability, low glass transition temperature, and high mechanical strength.
  • Aromatic polyaryl ether ketones have significant commercial utility, especially as molded articles and as composites with glass, carbon, or polyaramide fibers for a variety of structural applications including in the aerospace and general engineering industries.
  • the warpage and dimensional stability of these polymers, including PEEK have been improved by the use of fillers such as glass fiber, carbon fiber, talc, and mica.
  • additives and such as polyetherimide blends with PEEK have been used to inhibit the crystallization of PEEK, and hence to help improve transparency.
  • EP 2155820 (A1 ) discloses blends of PAEK with isoindolinone copolycarbonates and related articles.
  • US 20070219344 (A1 ) discloses high heat polyethersulfone compositions, methods for their preparation, and articles made therefrom.
  • US 20110151262 (A1 ) discloses thermoplastic high-T g polycarbonates and moulding materials which are distinguished by improved thermal properties and improved mechanical properties, in particular by reduced thermal expansion.
  • US 20110104417 discloses high temperature compositions of a first polymer blend of poly(aryl ether ketone phthalazinone)s and a second polymer blend of poly(aryl ether ketone)s, thermoplastic polyimides, poly(aryl ether sulfone)s, polybenzimidazoles, poly(phenylene sulfide)s and combinations thereof that have improved high temperature characteristics.
  • PAEKs have a relatively low glass transition temperature (Tg), for example 150 °C. This low Tg limits their load bearing capability at temperatures above the Tg, especially in compositions with no reinforcing fiber.
  • Tg glass transition temperature
  • the high crystallinity of PAEK results in high shrinkage during transition from the melt to the solid phase, which can produce warp or other unfavorable changes in dimension. It would therefore be desirable to prepare polyarylether ketone formulations having one or more improved properties, such as reduced warpage, improved dimensional stability, or improved transparency. It would be especially desirable if one or more of these properties could be obtained with at least one of a high melting point, chemical resistance, thermal stability, hydrostability, high glass transition temperature, or high mechanical strength.
  • a polymer composition comprises, based on the total weight of the polymers: 1-99 wt%, preferably 10-90 wt%, of a polymer component comprising a polyarylether ketone, a polybenzimdazole, a polyimide, a poly(aryl ether sulfone), a poly(phenylene sulfide), or a combination comprising at least one of the foregoing; and 1-99 wt%, preferably 10-90 wt%, of a polyisoindolinone, wherein the polyisoindolinone comprises: 1-100 mol%, preferably 5-100 mol%, of isoindolinone ether ketone units of the formula wherein each R 1 is independently the same or different, and is hydrogen, C 1-8 alkyl, C 3-8 cycloalkyl, or phenyl optionally substituted with 1-5 C 1-6 alkyl groups, each R a is independently the same or different, and is C 1-6 alkyl, each R
  • An article comprising the polymer composition is described.
  • a method of forming the article comprises shaping, extruding, molding, or injection molding the polymer composition is also described.
  • polymer compositions comprising polyaryl ether ketones comprising isoindolinone ether moieties and a second polymer component.
  • the polymers that contain isoindolinone ether ketone moieties are poly(isoindolinone ether ether ketone)s, poly(isoindolinone ether ether ketone ketone)s, and the like, which will be referred to collectively herein as "polyisoindolinones" for convenience.
  • the polyisoindolinones are melt processable, and have good high temperature properties, and can further have one or more of good transparency (clarity), good mechanical properties, low color, good hydrostability, and good chemical resistance.
  • the second polymer component has a high Tg (for example greater than 200 °C).
  • the combination of the polyisoindolinones and the high Tg second polymer component, such as other PAEKs, provides polymer compositions that can also have good high temperature properties, and can be melt processable and have one or more of good transparency (clarity), good mechanical properties, low color, good hydrostability, and good chemical resistance.
  • the polyisoindolinones comprise substantially or completely 100 mol% of isoindolinone ether ether ketone units of formula (1).
  • R 1 is hydrogen, C 1-8 alkyl, C 3-8 cycloalkyl, or phenyl optionally substituted with 1-5 C 1-6 alkyl groups.
  • R 1 is hydrogen, C 1-6 alkyl, C 3-6 cycloalkyl, or phenyl optionally substituted with 1-3 C 1-6 alkyl groups.
  • R 1 is hydrogen, C 1-3 alkyl, or unsubstituted phenyl. Most preferably, R 1 is unsubstituted phenyl.
  • the isoindolinone ether ether ketone units in the same polymer can have different R 1 groups, but preferably each R 1 is the same.
  • each R a is independently the same or different, and is C 1-6 alkyl, preferably C 1-4 alkyl, more preferably C 1-3 alkyl; and p is an integer of 0-4, preferably 0, 1, or 2, most preferably 0.
  • the isoindolinone ether ether ketone units in the same polymer can have different values of p, but preferably each value of p is the same.
  • each R b is independently the same or different, and is C 1-12 alkyl, C 2 - 12 alkenyl, C 3-8 cycloalkyl, or C 1-12 alkoxy, preferably C 1-6 alkyl, C 2-6 alkenyl, C 3-6 cycloalkyl, or C 1-6 alkoxy, more preferably C 1-3 alkyl, and most preferably methyl; and q is an integer of 0-4, preferably 0, 1, or 2, most preferably 0.
  • the isoindolinone ether ether ketone units in the same polymer can have different values of q, but preferably each value of q is the same.
  • the methyl group can be disposed ortho to the tetravalent carbon atom linking the phenoxy groups to the isoindolinones group.
  • each R c is independently the same or different, and is C 1-12 alkyl, C 2 - 12 alkenyl, C 3-8 cycloalkyl, or C 1-12 alkoxy, preferably C 1-6 alkyl, C 2-6 alkenyl, C 3-8 cycloalkyl, or C 1-12 alkoxy, more preferably C 1-3 alkyl, most preferably methyl; and r is an integer of 0-4, preferably 0-2, most preferably 0.
  • the isoindolinone ether ether ketone units in the same polymer can have different values of r, but preferably each value of r is the same.
  • x is an integer of 1-4, preferably 1-3, preferably 1 or 2.
  • the isoindolinone ether ether ketone units in the same polymer can have different values of x, but preferably each value of x is the same.
  • the polyisoindolinones contain poly(isoindolinone ether ether ketone) units when x is 1.
  • the polyisoindolinones contain poly(isoindolinone ether ether ketone ketone) units when x is 2, and so on.
  • R 1 is hydrogen, C 1-6 alkyl, C 3-6 cycloalkyl, or phenyl optionally substituted with 1-3 C 1-6 alkyl groups;
  • R a is C 1-4 alkyl;
  • each R b is independently the same or different, and is C 1-6 alkyl, C 2-6 alkenyl, C 3-6 cycloalkyl, or C 1-6 alkoxy;
  • each R c is independently the same or different, and is C 1-6 alkyl, C 2-6 alkenyl, C 3-8 cycloalkyl, or C 1-12 alkoxy;
  • each p is the same, and is 0 or 1, preferably 0;
  • each q is the same, and is 0 or 1, preferably 0;
  • each r is the same, and is 0 or 1, preferably 0; and
  • each x is an integer of 1-3, preferably 1 or 2.
  • R 1 is hydrogen, C 1-3 alkyl, or unsubstituted phenyl; each R a is C 1-3 alkyl; each R b is independently the same or different, and is C 1-3 alkyl, preferably methyl, each R c is independently the same or different, and is C 1-3 alkyl, preferably methyl, each p, q, and r is independently the same or different, and is an integer of 0, 1, or 2, preferably 0, and x is 1 or 2.
  • R 1 is phenyl, p, q, and r are each zero, and x is 1, providing the poly(N-phenyl isoindolinone ether ether ketone) of formula (1a) wherein z is the number of repeating units, and is greater than 1, for example 2-1,000, or 5-800, or 10-500, or 10-350.
  • R 1 is phenyl, p, q, and r are each zero, and x is 2, providing the poly(N-phenyl isoindolinone ether ether ketone ketone) of formula (1b). wherein z is the number of repeating units, and is greater than 1, for example 2-1,000, or 5-800, or 10-500, or 10-350.
  • the polyisoindolinones can comprise additional ether units.
  • the polyisoindolinones comprise 1-99 mole percent (mol%), preferably 5-95 mol%, or 70-99 mol%, or 1-70 mol% of isoindolinone ether ether ketone units of formula (1), and 1-99 mol%, preferably 5-95 mol%, 1-30 mol%, or 30-99 mol%, of arylene ether ketone units of formula (2), based on the total moles of units of formulas(1) and (2).
  • each R c is independently the same or different, and is C 1-12 alkyl, C 2 - 12 alkenyl, C 3-8 cycloalkyl, or C 1-12 alkoxy; preferably each R c is the same and is C 1-3 alkyl, preferably methyl; and each r is independently the same or different, and is an integer of 0-4, preferably 0-2, more preferably 0 or 1, still more preferably 0.
  • the arylene ether ketone units in the same polymer can have different values of r, but preferably each value of r is the same.
  • x is an integer of 1-4, preferably 1-3, more preferably 1 or 2.
  • the arylene ether ketone units in the same polymer can have different values of x, but preferably each value of x is the same.
  • the polyaryl ether ketones contain poly(aryl ether ether ketone) units when each x is 1.
  • the polyaryl ether ketones contain poly(aryl ether ether ketone ketone) units when x is 2.
  • each R 2 is independently the same or different, and is a C 6 - 30 substituted or unsubstituted arylene.
  • R 2 is a C 6 - 30 substituted or unsubstituted arylene of formula (3).
  • each R e is independently the same or different, and is C 1-12 alkyl, C 2-6 alkenyl, C 3-6 cycloalkyl, or C 1-6 alkoxy, preferably C 1-6 alkyl, C 2-6 alkenyl, C 3-6 cycloalkyl, or C 1-6 alkoxy, more preferably each R e is the same and is C 1-3 alkyl, most preferably methyl; and each t is independently the same or different, and is an integer of 0-4, preferably an integer of 0-2, and more preferably each t is the same, and is 0 or 1, most preferably 0.
  • Each R 2 in the same polymer can have different values of t, but preferably each value of t is the same.
  • each u is independently the same or different, and is an integer of 0-4, preferably 0-2, and more preferably each u is the same and is 0 or 1.
  • Each R 2 in the same polymer can have different values of t, but preferably each value of t is the same.
  • R is a C 1-6 alkyl or phenyl
  • Each R 2 in the same polymer can have the same X a , or two different X a groups, or three different X a groups. In an embodiment, each R 2 in the same polymer has the same X a group.
  • R 2 groups include those derived from p -hydroquinone, methyl hydroquinone, dimethyl hydroquinone, tert-butyl hydroquinone, di-tert-butyl hydroquinone, resorcinol, 4,4'-biphenol, 4,4'-dihydroxydiphenyl ether, 4,4'-isopropylidenediphenol (also known as bisphenol A, or BPA), bis(3,5-dimethyl-4-hydroxyphenyl)isopropylidene,4,4'-(hexafluoroisopropylidene)diphenol, 4,4'-(hexafluoroisopropylidene)diphenol, bis(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl) sulfide, bis(3,5-dimethyl-4-hydroxyphenyl) sulfone, 4,4'-(
  • the mole ratios of the isoindolinone ether ether ketone units (1) to the arylene ether ketone units (2) can vary widely, depending on the desired characteristics of the polymer, ease of synthesis, cost, and like considerations. As stated above, the mole ratio of isoindolinone ether ether ketone units (1) : arylene ether ketone units (2) can be from 1:99 to 99:1, or from 5:95 to 95:5. In some embodiments the mole ratio of units (1) : units (2) can be 10:90 to 90:10, or 20:80 to 80:20, or 30:70 to 70:30, or 40:60 to 60:40.
  • the mole ratio of units (1) : units (2) can be from 50:50 to 99:1, or from 60:40 to 95:5, or 70:30 to 90:10.
  • the mole ratio of units (1) : units (2) can be from 1:99 to 50:50, or 5:95 to 40:60, or 10:90 to 30:70.
  • R 1 is hydrogen, C 1-6 alkyl, C 3-6 cycloalkyl, or phenyl optionally substituted with 1-3 C 1-6 alkyl groups;
  • R a is C 1-4 alkyl;
  • each R b is independently the same or different, and is C 1-6 alkyl, C 2-6 alkenyl, C 3-6 cycloalkyl, or C 1-6 alkoxy;
  • each R c is independently the same or different, and is C 1-6 alkyl, C 2-6 alkenyl, C 3-8 cycloalkyl, or C 1-12 alkoxy;
  • each R c is independently the same or different, and is C 1-6 alkyl, C 2-6 alkenyl, C 3-6 cycloalkyl, or C 1-6 alkoxy;
  • each p, q, r, s
  • R 1 is hydrogen, C 1-3 alkyl, or unsubstituted phenyl; each R a is the same C 1-3 alkyl; each R b is the same C 1-3 alkyl, preferably methyl; each R c is the same C 1-3 alkyl, preferably methyl; each R c is the same C 1-3 alkyl, preferably methyl; each p, q, r, s, and t is independently the same or different, and is an integer of 0 or 1, preferably 0; each u is independently the same or different, and is 0 or 1; each x is the same, and is 1 or 2.
  • a method for the synthesis of the foregoing polyisoindolinones is described.
  • the synthesis proceeds via nucleophilic substitution.
  • This and other processes for the manufacture of the polyisoindolinones are described, for example, in U.S. Pat. No. 4,176,222 .
  • a polyisoindolinone comprising isoindolinone ether ether ketone units of formula (1) can be obtained in a polymerization reaction of a dihydroxy isoindolinone compound of formula (4) with a dihalogenated aromatic compound of formula (5) in a liquid-phase polymerization mixture that further comprises a base.
  • each X formula (5) is independently the same or different, and is a halogen, preferably fluorine or chlorine.
  • a polyisoindolinone comprising isoindolinone ether ether ketone units (1) and arylene ether ketone units (2) can be made by further including a dihydroxy arylene compound of formula (6) in the polymerization mixture.
  • the variable R 2 in formula (6) is as defined in formula (2) and (2a).
  • the relative amount of dihydroxy isoindolinone compound (4) to dihydroxy arylene compound (6) depends on the relative reactivity of the dihydroxy compounds, the order of addition, the desired mole ration in the polymer, and like considerations.
  • the amount of dihydroxy isoindolinone compound (4) is 1-100 mol%, preferably 5-100 mol%
  • the amount of dihydroxy arylene compound (6) is 0-99 mol%, preferably 5-95 mol%, each based on the total moles dihydroxy isoindolinone compound (4) and dihydroxy arylene compound (6) (referred to collectively herein as "the dihydric monomer composition").
  • the relative molar ratio of dihydroxy isoindolinone compound (4) to dihydroxy arylene compound (6) can be 10:90 to 90:10, or 20:80 to 80:20, or 30:70 to 70:30, or 40:60 to 60:40; or, to control crystallinity, 70:30 to 100:0 (to obtain a crystalline polymer) or 1:99 to 70:30 (to obtain a noncrystalline polymer).
  • the mole ratio of hydroxy isoindolinone compound (4) and dihydroxy arylene compound (6) can be from 50:50 to 99:1, or from 60:40 to 95:5, or 70:30 to 90:10.
  • the mole ratio of hydroxy isoindolinone compound (4) and dihydroxy arylene compound (6) can be from 1:99 to 50:50, or 5:95 to 40:60, or 10:90 to 30:70.
  • conditions for the formation of the poly(isoindolinone) can be varied depending on considerations such as the reactivity of the reactants, desired yields and purity, efficiency, and cost.
  • the hydroxy isoindolinone compound (4) can have less than 1000 ppm, or less than 800 ppm, or less than 500 ppm each of a monoaminophenol of formula (7a) or a phenolphthalein compound of formula (7b).
  • each variable is the same as in formula (1) or (1a).
  • the amount of the monoaminophenol (7a) or phenolphthalein compound (7b) can each be determined by liquid chromatography analysis as is known in the art.
  • the base is selected to increase the rate of polymerization, and can be selected based on the specific reactants, solvent, and polymerization conditions.
  • the base can be an alkali or alkaline earth metal hydroxide, alkali or alkaline earth metal carbonate, alkali or alkaline earth metal bicarbonate, or a combination comprising at least one of the foregoing.
  • the base is sodium hydroxide, potassium hydroxide, sodium carbonate, cesium hydroxide, potassium carbonate, cesium carbonate, strontium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or a combination comprising at least one of the foregoing.
  • an organic solvent can be present that is effective to dissolve the reactants.
  • organic solvents include diphenylsulfone, dimethyl sulfone, sulfolane, N-methyl-caprolactam, N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl acetamide, dimethyl formamide, diphenylether, tetramethylurea, N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, or a combination comprising at least one of the foregoing.
  • a cosolvent can be present during the polymerizing, for example for the purpose of azeotropic distillation of water from the polymerization mixture.
  • the cosolvent can be an aromatic hydrocarbon, preferably toluene, xylene, ortho-dichlorobenzene, trichlorobenzene, or mesitylene, or an aliphatic hydrocarbon, preferably cyclohexane.
  • the reactant content (also referred to as "solids content”) in the liquid-phase polymerization mixture can vary depending on the reactants, polymerization conditions, and equipment used to conduct the polymerization.
  • the solids content can be 25-80% by weight, based on the total weight of the polymerization mixture.
  • the polymerization is conducted under conditions effective to promote the nucleophilic substitution.
  • the polymerization can be conducted for 1-24 hours, or 2 to 12 hours, or 2 to 6 hours.
  • the polymerization can be conducted at atmospheric pressure, or greater than atmospheric pressure, for example up to 10 bar
  • the polymerization can be conducted under an inert atmosphere, for example under nitrogen or argon.
  • the polymerization can be conducted at room temperature, but is preferably heated, for example to a temperature of 50-400 °C, or 80-400 °C.
  • a multi-step heating regime is used, for example heat at to a temperature greater than 100 °C, and less than the decomposition temperature of the reactants, the solvent, and the polymer for a first time period, followed by heating at 200-350 °C for a second time period until the polymerization has proceed to the desired degree of completion.
  • the relative molar ratio of the dihydric monomer composition (isoindolinone ether ether ketone units (1) and arylene ether ketone units (2) (if present)) to the dihalogenated aromatic compound (5) can be varied depending on the reactivity of the reactants, order of addition, and like polymerization considerations. In some embodiments the molar ratio of the dihydric monomer composition to the dihalogenated aromatic compound (5) is 1.8:2.2 to 2.2:1.8, or 1.9:2:1, or 1.95:2.05 to 2.05:1.95.
  • the dihydroxy isoindolinone compound (4), the dihydroxy arylene compound (6), or both are converted to the corresponding alkali or alkaline earth metal salts before or during contacting with the dihalogenated aromatic compound (5).
  • the monomers of the dihydric monomer composition are at least partially, preferably substantially completely or completely, converted to the corresponding alkali or alkaline earth metal salts (8) or (9) M +- O-R 2 -O -+ M (9) to provide a dialkali or alkaline earth metal salt composition.
  • the variable in formulas (8) and (9) are as defined in formulas (1), (1a), (2), and (2a). Conversion to the salt can be effected by pre-contacting the dihydroxy isoindolinone compound (4), the dihydroxy arylene compound (6), or both with the base used in the polymerization.
  • the dialkali or alkaline earth metal salt composition is formed in situ by reacting the dihydroxy isoindolinone compound (4), the dihydroxy arylene compound (6), or both in the presence of an alkali or alkaline earth metal source, under conditions effective to form the dialkali or alkaline earth metal salts, preferably wherein the alkali or alkaline earth metal source is provided in an amount of 0.5-1.05 molar equivalent per mole of hydroxy group.
  • the alkali or alkaline earth metal source can be an alkali or alkaline earth metal hydroxide, alkali or alkaline earth metal carbonate, alkali or alkaline earth metal bicarbonate, or a combination comprising at least one of the foregoing.
  • the alkali or alkaline earth metal source is sodium hydroxide, potassium hydroxide, sodium carbonate, cesium hydroxide, potassium carbonate, cesium carbonate, strontium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or a combination comprising at least one of the foregoing.
  • the method can further comprise dehydrating the alkali or alkaline earth metal salt composition to remove water before, during, or after introduction of the dihalogenated aromatic compound (5).
  • Dehydrating can be by one or more of azeotropic distillation in the presence of suitable co-solvent or in the presence of inert gas atmosphere sweep, preferably nitrogen, argon, or a combination comprising at least one of the foregoing.
  • dehydration is conducted before heating the polymerization mixture to a temperature greater than 100 °C, and less than the decomposition temperature of the reactants, the solvent, and the polymer; and then preferably heating the polymerization mixture from 200-350 °C until the polymerization has proceed to the desired degree of completion.
  • a water content of the liquid-phase polymerization mixture is maintained at less than 0.5 wt%, or less than 0.25 wt%, based on the total weight of the polymerization mixture.
  • the water content can be maintained as this level by azeotropic distillation in the presence of suitable co-solvent or in the presence of inert gas atmosphere sweep, preferably nitrogen, argon, or a combination comprising at least one of the foregoing.
  • the polymerizing can be in the presence of an end capping agent, preferably 1.5-4 mol% of an end capping agent, based on the total moles of dihydric monomer.
  • the end capping agent can be a monohydric compound, a monohalide compound, a monoacyl halide, or a combination comprising at least one of the foregoing.
  • the monohydric compound or monohalide compound is aromatic.
  • the monohydric compound can be phenol, p -tertbutyl phenol, p -cumylphenol, 4-phenylphenol, or 4-hydroxybenzophenone;
  • the monohalide compound can be a C 1-12 alkyl halide or C 6-12 aryl halide; and
  • the monoacyl halide can be a C 2 - 12 alkyl acyl halide or C 6-12 aryl acyl halide.
  • the end capping agent can be added at the beginning, during, or at the end of the polymerization, but more preferably the end capping agent is added at the beginning or during the polymerization.
  • the progress of the polymerization can be monitored by a number of methods, for example by monitoring a polymer hydroxyl end group content, or polymer halogen content, or polymer molecular weight change.
  • the hydroxyl end group content of the polymer can be determined by various titration and spectroscopic methods well known in the art. Spectroscopic methods include infrared, nuclear magnetic resonance (NMR), Raman spectroscopy, and fluorescence. Examples of infrared methods are described in J, A. Kreuz, et al, J. Poly. Sci. Part A-1, vol. 4, pp. 2067 2616 (1966 ). Examples of titration methods are described in Y. J. Kim, et al, Macromolecules, vol. 26, pp. 1344 1358 (1993 ). It may be advantageous to make derivatives of polymer end groups to enhance measurement sensitivity using variations of methods as described in K. P. Chan et al., Macromolecules, vol.
  • the polymerization is continued until the resultant polyisoindolinone has a hydroxyl end group content of less than 700 parts per million by weight (ppm) of the polymer, or less than 500 ppm.
  • the halogen end group content of the polymer can be determined by NMR spectroscopy or ion chromatography after combustion, for example.
  • the polymerization is continued until the resultant polyisoindolinone has a halogen end group content of less than 900 ppm, or less than 700 ppm.
  • the polymerization is continued until the resultant polyisoindolinone has a weight average molecular weight (Mw) change of less than 500 Daltons/hour, or less than 300 Daltons/hour.
  • the polymerization is continued until the resultant polyisoindolinone has a weight average molecular weight (Mw) change of less than 500 Daltons/hour, or less than 300 Daltons/hour.
  • Mw can be determined, for example, by The Mw can be determined, for example, by light scattering, inherent viscosity (IV) techniques, or gel permeation chromatography (GPC) using polystyrene standards and aggressive solvents such as those used for polyphenylene sulfide (e.g., o-chloro naphthalene) or PEEK (e.g, 80% chloroform with 20% dichloroacetic acid).
  • polyphenylene sulfide e.g., o-chloro naphthalene
  • PEEK e.g, 80% chloroform with 20% dichloroacetic acid
  • the polyisoindolinones can be separated from the polymerization mixture by methods known in the art, for example by decanting, centrifuging, or extracting.
  • the as-synthesized polyisoindolinones can be further purified by methods known in the art, for example by extracting, precipitating, washing, or crystallizing.
  • the above methods for the manufacture of the poly(isoindolinone ether ether ketone)s in particular provide polymers having at least one, preferably at least two, preferably all of the following properties: a glass transition temperature greater than 150 °C, or 150-270 °C as determined by differential scanning calorimetry; less than 20 weight percent (wt%) solubility at 23 °C in dichloromethane, ortho-dichlorobenzene, or chloroform, or substantially no blue phosphorescence in response to irradiation with ultraviolet light of 320-400 nm.
  • the above methods provide poly(isoindolinone ether ether ketone)s of higher molecular weight, or greater purity. These polymers are accordingly more suitable for use in articles requiring one or more of improved chemical resistance, improved heat resistance, improved mechanical properties, improved transparency, or higher Tg.
  • the properties of the polyisoindolinones can be varied to suit the particular application, by varying the type of units, including any substituents on the units, the relative amount of each type of unit, and the method of manufacture of the polyisoindolinones.
  • the polyisoindolinones in particular the poly(isoindolinone ether ether ketone)s, can have a glass transition temperature greater than 150 °C, or 150-300 °C, or 150-270 °C as determined by differential scanning calorimetry, using a heating and cooling ramp of 20 °C/minute.
  • the polyisoindolinones can have less than 25 wt%, or less than 15 wt%, or less than 5 wt%, or less than 1 wt% solubility at 23 °C in dichloromethane, orthodichlorobenzene, or chloroform.
  • the polyisoindolinones can have less than 25 wt%, or less than 15 wt%, or less than 5 wt%, or less than 1 wt% solubility at 23 °C in 1,1,1,3,3,3-hexafluoro-2-propanol, N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl acetamide, dimethyl formamide, m -cresol, o-dichlorobenzene, 1,3,5-trichlorobenzene, a mixture comprising phenol and trichloroethane, or a combination comprising at least one of the foregoing.
  • the polyisoindolinones in particular the poly(isoindolinone ether ether ketone)s, can have no, or substantially no, blue phosphorescence in response to irradiation with ultraviolet light of 320-400 nm.
  • the polyisoindolinones in particular the poly(isoindolinone ether ether ketone)s, can have less than 25 ppm, or less than 20 ppm, or less than 10 ppm, of benzylic protons based on the weight of the polyisoindolinone, which can be determined using ordinary chemical analysis for example proton NMR spectroscopy.
  • the polymer is free or substantially free of linkages that can react in the melt to change the molecular weight of the polymer. The presence of benzylic protons in the polyisoindolinone can accelerate reactions that change molecular weight in the melt.
  • polyisoindolinones with structural units derived from monomers and capping agents essentially free of benzylic protons are desirable in some applications, especially those involving isolation from the melt and melt processing after polymerization.
  • substantially or essentially free of benzylic protons means that the polyisoindolinone has less than or equal to 5 mole % of structural units, or less than or equal to 3 mole % structural units, or less than or equal to 1 mole % structural units derived containing benzylic protons.
  • Free of benzylic protons means that the polyisoindolinone has zero mole % of structural units derived from monomers and end cappers containing benzylic protons.
  • the polyisoindolinones in particular the poly(isoindolinone ether ether ketone)s, can have a hydroxyl polymer end group content of less than 700 ppm, or less than 500 ppm, or less than 300 ppm based on the weight of the polyisoindolinone, which can be determined by various titration and spectroscopic methods well known in the art as described above.
  • Low hydroxyl group content can provide compositions having improved thermal properties, for example long term heat aging at elevated temperatures (e.g., above 100°C).
  • the polyisoindolinones in particular the poly(isoindolinone ether ether ketone)s, can have a halogen content of less than 900 ppm, or less than 700 ppm, based on the weight of the polyisoindolinone, which can be determined by ordinary chemical analysis; for example combustion followed by ion chromatogram or ICP atomic emission spectroscopy. Polymers free of halogen atoms are sometimes desired for regulatory and environmental reasons. In an embodiment the polyisoindolinone is essentially free of halogen atoms.
  • Essentially free of halogen atoms means that the polyisoindolinone has less than or equal to 5 mole % of structural units, or, more specifically, less than or equal to 3 mole % of structural units, or, even more specifically, less than or equal to 1 mole % of structural units derived from compounds containing halogen atoms.
  • the polyisoindolinones in particular the poly(isoindolinone ether ether ketone)s, can have a residual alkali or alkaline earth metal cation content of less than 500 ppm, or less than 300 ppm, based on the weight of the polyisoindolinone, which can be determined by ion chromatography or inductively coupled plasma mass spectroscopy (ICP-MS).
  • ICP-MS inductively coupled plasma mass spectroscopy
  • Low alkali or alkaline earth metal content can provide improved electrical properties, for example a low comparative tracking index (CTI).
  • CTI comparative tracking index
  • the polyisoindolinones in particular the poly(isoindolinone ether ether ketone)s, can have a residual solvent content of less than 500 ppm, or less than 250 ppm, or less than 100 ppm based on the weight of the polyisoindolinone, which can be determined by gas or liquid chromatography. Polymers having low solvent content are sometimes desired for regulatory and environmental reasons and to achieve molded parts with reduced surface defects such as mold-splay or plate-out.
  • the polyisoindolinones in particular the poly(isoindolinone ether ether ketone)s, can have a weight average molecular weight of at least 15,000 Daltons, preferably 20,000-100,000 Daltons, more preferably 20,000-60,000 Daltons, as measured by gel permeation chromatography ( GPC ) or IV techniques as described above.
  • the polyisoindolinones in particular the poly(isoindolinone ether ether ketone)s, can have an onset decomposition temperature of greater than 485°C as determined using thermogravimetric analysis in air and nitrogen.
  • the polyisoindolinones in particular the poly(isoindolinone ether ether ketone)s, can have a coefficient of thermal expansion of 30-90 ppm/°C, or 30-60 ppm/°C, or 40-60 ppm/°C, as determined according to ASTM E 831.
  • the polyisoindolinones in particular the poly(isoindolinone ether ether ketone)s, can have a water uptake of less than 3 percent, preferably less than 1 percent, most preferably less than 0.6 percent at 23°C, after 24 hours of direct immersion.
  • the polyisoindolinones in particular the poly(isoindolinone ether ether ketone)s, can have a shift in melt viscosity of less than 30% over 30 min at 380 C under a nitrogen atmosphere as measured in a small amplitude oscillatory time sweep rheology at a fixed angular frequency of 10 radians/second.
  • the polyisoindolinones in particular the poly(isoindolinone ether ether ketone)s, can have a char yield of greater than 30 wt%, as determined using thermogravimetric analysis under inert atmosphere of nitrogen.
  • the polyisoindolinones in particular the poly(isoindolinone ether ether ketone)s, can have a melt-pressed film of 50-500 micrometer ( ⁇ m) thickness, or 300 ⁇ m thickness, can be folded 180 degrees more than 3 times without breaking.
  • the polyisoindolinones in particular the poly(isoindolinone ether ether ketone)s, can have a melt-pressed film of 50-500 ⁇ m thickness, or 300 ⁇ m thickness, can be folded 180 degrees greater than 3 times without breaking after autoclaving for 3 days at 130°C.
  • the polyisoindolinones, in particular the poly(isoindolinone ether ether ketone)s can have a melt-pressed film of 50-500 ⁇ m thickness, or 300 ⁇ m thickness, can be folded 180 degrees greater than 3 times without breaking after autoclaving for 3 days at 130°C.
  • the polyisoindolinones in particular the poly(isoindolinone ether ether ketone)s, can have a modulus of greater than 1000 MPa at 150-300 °C, as measured by ASTM D5418, on a film having a thickness of 150-500 ⁇ m, or 300 ⁇ m.
  • a 150-500 ⁇ m- or 300 ⁇ m-thick molded sample of the polymer compositions has at least 70% transmission at 850 nm, 1310 nm, or 1550 nm as measured on an ultraviolet-visible/near infrared spectrophotometer ; or a 150-500 ⁇ m-thick molded sample of the polymer compositions has greater than 70% transmission as measured using the color space CIE1931 (Illuminant C and a 2° observer).
  • the polymer compositions further comprise a second polymer that is not the same as the polyisoindolinones.
  • the second polymer also has good heat resistance.
  • Such polymers can be a polyarylether ketone, a polybenzimidazole, a polyimide, a poly(aryl ether sulfone), a poly(phenylene sulfide), or a combination comprising at least one of the foregoing.
  • the polymer to be combined with the polyisoindolinone is a polyarylether ketone (PAEK).
  • PAEK polyarylether ketone
  • PAEKs include several polymer types containing aromatic rings, such as phenyl rings, linked primarily by ketone and ether groups in different sequences.
  • PAEKs are polyether ketones (PEK), polyether ether ketones (PEEK), polyether ketone ether ketone ketones (PEKEKK) and polyether ketone ketones (PEKK) and copolymers containing such groups.
  • the PAEKs can include monomer units containing an aromatic ring, such as a phenyl ring, a keto group, and an ether group in any sequence.
  • polyarylether ketone as used herein further includes homopolymers, copolymers, terpolymers, graft copolymers, and the like.
  • Polyarylether ketones can include arylene ether ketone units of formula (2).
  • polyarylether ketones that are highly crystalline, with melting points above 300 °C can be used in the polyisoindolinone compositions. Examples of these crystalline polyarylether ketones contain units shown in the structures (10)-(14).
  • compositions of two or more PAEK polymers can also be used.
  • the polyarylether ketones can have an Mw of 5,000 to 150,000 g/mole, or 10,000-80,000 g/mole.
  • Polyarylether ketone)s can be prepared by methods well known in the art. Such processes are described for example, in U.S. Patent Nos. 4,176,222 ; 4,396,755 ; 4,398,020 ; and 4,175,175 .
  • Exemplary PEEKs include those commercially available from Victrex Ltd. as VICTREX® PEEK.
  • Exemplary PEKEKKs include those that are commercially available from BASF Co. as ULTRAPEK®.
  • the second polymer component in the polymer composition can be an aromatic benzimidazole (PBI).
  • PBI aromatic benzimidazole
  • Processes for the preparation of aromatic polybenzimidazoles are described in a number of U.S. Pat. Nos. 3,901,855 ; 4,002,679 ; 3,433,772 ; 3,441,640 ; and 4,020,142 .
  • Aromatic PBI is commercially available from PBI Performance Products Inc as CELAZOLE® PBI polymer and has units of the formula (16).
  • the second polymer component in the polymer composition can be a polyimide such as a polyetherimide (PEI) and copolymers thereof.
  • PEI polyetherimide
  • Polyimides comprise more than 1, for example 1-1000, or 1-500, or 10 to 100, structural units of formula (17) wherein each V is the same or different, and is a substituted or unsubstituted tetravalent C 4-40 hydrocarbon group, for example a substituted or unsubstituted C 6-20 aromatic hydrocarbon group, a substituted or unsubstituted, straight or branched chain, saturated or unsaturated C 2-20 aliphatic group, or a substituted or unsubstituted C 4-8 cycloalkylene group or a halogenated derivative thereof, in particular a substituted or unsubstituted C 6-20 aromatic hydrocarbon group.
  • R is m-phenylene, p-phenylene, or a diaryl sulfone.
  • Polyetherimides are a class of polyimides that comprise more than 1, for example 10-1000, or 10-500, structural units of formula (19) wherein each R is the same or different, and is as described in formula (17).
  • T is -O- or a group of the formula -O-Z-O-wherein the divalent bonds of the -O- or the -O-Z-O- group are in the 3,3', 3,4', 4,3', or the 4,4' positions.
  • the group Z in -O-Z-O- of formula (1) is a substituted or unsubstituted divalent organic group, and can be an aromatic C 6-24 monocyclic or polycyclic moiety optionally substituted with 1-6 C 1-8 alkyl groups, 1-8 halogen atoms, or a combination comprising at least one of the foregoing, provided that the valence of Z is not exceeded.
  • Exemplary groups Z include groups derived from a dihydroxy compound of formula (3) as described above.
  • Z is derived from bisphenol A.
  • R is m-phenylene or p-phenylene and T is -O-Z-O- wherein Z is derived from bisphenol A.
  • the polyetherimide can be a copolymer, for example, a polyetherimide siloxane, or a polyetherimide sulfone copolymer comprising structural units of formula (17) wherein at least 50 mol% of the R groups are of formula (18) wherein Q 1 is -SO 2 - and the remaining R groups are independently p-phenylene or m-phenylene or a combination comprising at least one of the foregoing; and Z is 2,2'-(4-phenylene)isopropylidene.
  • a copolymer for example, a polyetherimide siloxane, or a polyetherimide sulfone copolymer comprising structural units of formula (17) wherein at least 50 mol% of the R groups are of formula (18) wherein Q 1 is -SO 2 - and the remaining R groups are independently p-phenylene or m-phenylene or a combination comprising at least one of the foregoing; and Z is 2,2'-(
  • the polyetherimides have an Mw of 1,000-150,000 grams/mole (Dalton), or 10,000-80,000 Daltons, as measured by gel permeation chromatography, using polystyrene standards.
  • Polyetherimides are commercially available from SABIC as ULTEM, EXTEM, and SILTEM.
  • the second polymer component in the polymer composition can be a poly(aryl ether sulfone) such as poly(phenylene sulfone) (PPSU) and copolymers thereof.
  • PPSU poly(phenylene sulfone)
  • Processes for the preparation of poly(aryl ether sulfone) are described in U.S. Pat. Nos. 4,108,837 and 6,228,970 .
  • Poly(aryl ether sulfone) is commercially available from Solvay Advanced Polymers LLC as RADEL® 5000 and can have units of formula (21).
  • the second polymer component in the polymer composition can be a poly(phenylene sulfide) and copolymers.
  • Processes for the preparation of poly(phenylene sulfide) are described in a number of U.S. Pat. Nos. 4,464,507 and 5,071,949 .
  • Poly(phenylene sulfide) is commercially available from Ticona as FORTRON® PPS and can have the general structure (22).
  • the ratio of the polyisoindolinone to the second polymer component in the polymer composition can be any that results in a polymer composition that has the desired properties.
  • the ratio, in parts by weight, of polyisoindolinone to the second polymer component can be from 1:99 to 99:1, depending on the end use application, and the desired properties.
  • the ratios can be from 15:85 to 85:15 or from 25:75 to 75:25, or from 40:60 to 60:40.
  • compositions of the polyisoindolinones in particular the poly(isoindolinone ether ether ketone)s, can further comprise an additive composition, a filler, a reinforcing agent, or a combination comprising at least one of the foregoing.
  • An additive composition comprising one or more additives selected to achieve a desired property can be present in the polymer composition, with the proviso that the additives are also selected so as to not significantly adversely affect a desired property of the polymer composition.
  • Additives that have high temperature resistance and low volatility are preferred.
  • the additives are selected to have a molecular weight of above 500 g/mol.
  • the additive composition or individual additives can be mixed at a suitable time during the mixing of the components for forming the composition.
  • the additive can be soluble or non-soluble in the polyisoindolinone, and can include an anti-drip agent (e.g., a PTFE-encapsulated styrene-acrylonitrile copolymer (TSAN)), anti-fog agent, antimicrobial agent, antioxidant, antistatic agent, blowing agent, colorant (e.g, a dye or pigment), flame retardant, flow modifier, heat stabilizer, impact modifier, light stabilizer, lubricant, nucleating agent, plasticizer, processing aid, release agent (such as a mold release agent), surface effect additive, radiation stabilizer, ultraviolet light stabilizer, ultraviolet light absorber, or a combination comprising one or more of the foregoing.
  • an anti-drip agent e.g., a PTFE-encapsulated styrene-acrylonitrile copolymer (TSAN)
  • anti-fog agent e.g., antimicrobial agent, antioxidant, antistatic agent, blowing agent, colorant (e.g
  • each additive is used in an amount generally known to be effective.
  • the total amount of the additive composition (other than any impact modifier, filler, or reinforcing agent) can be 0.001-10.0 wt%, or 0.01-5 wt%, each based on the total weight of the polymer in the composition.
  • pigments include titanium dioxide and carbon black.
  • nucleating agents such as talc, clay, silica, carbon black, metal salts of long-chain (C16 or higher) carboxylic acids (e.g., sodium stearate, calcium oleate, potassium behenate, aluminum stearate and the like) or any combination thereof may be added.
  • talc long-chain carboxylic acids
  • metal salts of long-chain carboxylic acids e.g., sodium stearate, calcium oleate, potassium behenate, aluminum stearate and the like
  • 0.1-1.0% of talc with particle size of less than 5 ⁇ m is preferred.
  • the polymer compositions comprising the polyisoindolinones, the second polymer components, an additive, and optionally a reinforcing agent can be used in the manufacture of a composite.
  • Composites generally contain a polymer composition and a reinforcing agent. As is known in the art, some overlap exists between materials that can be used as fillers and those that can be used as reinforcing agents. In some embodiments a material can function as both a filler and a reinforcing agent.
  • the following lists of fillers and reinforcing agents are exemplary only, and not intended to be exclusive.
  • Possible fillers include, for example, silicates and silica powders such as aluminum silicate (mullite), synthetic calcium silicate, zirconium silicate, fused silica, crystalline silica graphite, natural silica sand, or the like; boron powders such as boron-nitride powder, boron-silicate powders, or the like; oxides such as TiO 2 (which can also be used as a pigment), aluminum oxide, magnesium oxide, or the like; calcium sulfate (as its anhydride, dihydrate or trihydrate); calcium carbonates such as chalk, limestone, marble, synthetic precipitated calcium carbonates, or the like; wollastonite; surface-treated wollastonite; glass spheres such as hollow and solid glass spheres, silicate spheres, cenospheres, aluminosilicate (armospheres), or the like; kaolin, including hard kaolin, soft kaolin, calcined kaolin, kaolin comprising various coating
  • Possible reinforcing agents include, for example, talc, including fibrous, modular, needle shaped, lamellar talc, or the like; mica; clays, including exfoliated nanoclays; single crystal fibers or "whiskers” such as silicon carbide, aluminum oxide, boron carbide, iron, nickel, copper, or the like; fibers (including continuous and chopped fibers) such as asbestos, carbon fibers, glass fibers, such as E, A, C, ECR, R, S, D, or NE glasses, or the like; metals and metal oxides such as fibrous aluminum, bronze, zinc, copper and nickel or the like; flaked fillers such as glass flakes, flaked silicon carbide, aluminum diboride, aluminum flakes, steel flakes or the like; inorganic fibrous materials, for example short inorganic fibers such as potassium titanate fiber, gypsum fiber, aluminum oxide fiber, magnesium oxide fiber, aluminum silicate fiber, and those derived from compositions comprising at least one of aluminum silicates, aluminum oxides, magnesium oxide
  • the reinforcing agent can be provided in the form of monofilament or multifilament fibers and can be used individually or in combination with other types of fiber, for example by co-weaving, core/sheath, side-by-side, orange-type or matrix and fibril constructions, or by other suitable methods.
  • Co-woven structures include glass fiber-carbon fiber, carbon fiber-aromatic polyimide (aramid) fiber, and aromatic polyimide fiberglass fiber or the like.
  • Fibrous fillers can be supplied in the form of, for example, rovings, woven fibrous reinforcements, such as 0-90 degree fabrics or the like; non-woven fibrous reinforcements such as continuous strand mat, chopped strand mat, tissues, papers and felts or the like; or three-dimensional reinforcements such as braids.
  • Preferred reinforcing agents are fibrous, and include glass fiber (such as E, A, C, ECR, R, S, D, or NE glasses), carbon fiber, polyaramide fiber, poly(p-phenylene-2,6-benzobisoxazole) fiber, carbon microfiber, carbon nanofiber, potassium titanate fiber, gypsum fiber, aluminum oxide fiber, aluminum silicate fiber, magnesium oxide fiber, or a combination comprising at least one of the foregoing fibers.
  • glass fiber such as E, A, C, ECR, R, S, D, or NE glasses
  • carbon fiber such as E, A, C, ECR, R, S, D, or NE glasses
  • polyaramide fiber such as E, A, C, ECR, R, S, D, or NE glasses
  • poly(p-phenylene-2,6-benzobisoxazole) fiber such as E, A, C, ECR, R, S, D, or NE glasses
  • carbon fiber such as E, A, C, ECR, R,
  • the fillers and reinforcing agents can be coated with a layer of metallic material to facilitate conductivity, or surface-treated with silanes to improve adhesion and dispersion with the polymer matrix.
  • Fillers and reinforcing agents can be generally used in amounts of 10-200 parts by weight, based on 100 parts by weight of the polymer.
  • polymer compositions also referred to herein as "polymer compositions” or “blend compositions”
  • blend compositions can have at least one of the following properties: a crystallinity of 10% or higher, or 20% or higher, as determined by differential scanning calorimetry; or less than 25 wt% solubility at 23 °C in dichloromethane, dichloroethane, or chloroform, when in the form of a melt-pressed film.
  • the polyisoindolinone blend compositions in particular the poly(isoindolinone ether ether ketone)s blended with a PEEK can have 10% crystallinity or higher, or 20% crystallinity or higher, as determined using differential scanning calorimetry on the second heat cycle, wherein heating and cooling is at a rate of 20 °C/minute for both heating and cooling cycles.
  • the polyisoindolinone compositions, in particular the poly(isoindolinone ether ether ketone)s blended with a PEEK can have less than 10% crystallinity, or less than 5% crystallinity, or no crystallinity for certain applications.
  • the relative ratio of isoindolinone ether ether ketone units (1) to arylene ether ketone units (2) can be adjusted to obtain the desired crystallinity in the polymer compositions.
  • 70-100 mol% of isoindolinone ether ether ketone units, based on the total units in the polyisoindolinones, can be used to obtain crystalline blend compositions that contain the polyisoindolinones and the second polymer.
  • 1-70 mol% isoindolinone ether ether ketone units can be used to obtain noncrystalline blend compositions that contain the polyisoindolinones and the second polymer.
  • a melt-pressed film comprising the polymer compositions can be folded 180 degrees greater than 3 times without breaking after autoclaving for 3 days at 130°C.
  • a 150-500 ⁇ m- or 300 ⁇ m-thick molded sample of the polymer compositions has at least 70% transmission at 850 nm, 1310 nm, or 1550 nm as measured on an ultraviolet-visible/near infrared spectrophotometer ; or a 150-500 ⁇ m- or 300 ⁇ m-thick molded sample of the polymer compositions has greater than 70% transmission as measured using the color space CIE1931 (Illuminant C and a 2° observer).
  • the polymer compositions can be immiscible, which have one or more of the following properties: a crystalline melting point of 300-350 °C as measured by differential scanning calorimetry per ASTM D3418 , two glass transitions between 150 and 300 °C as measured by differential scanning calorimetry per ASTM D3418 , or a modulus at 150-300 °C of greater than 300 MPa at 150-500 ⁇ m or 300 ⁇ m sample thickness measures according to ASTM D5418.
  • the immiscible compositions comprise a poly(isoindolinones ether ether ketone) homopolymer and a polyether ether ketone such as VICTREX PEEK available from Victrex Ltd., where the weight ratio of the poly(isoindolinones ether ether ketone) to the PEEK is 4:1 to 1:4 or 1:1 to 1:4.
  • the poly(isoindolinones ether ether ketone) homopolymer can be derived from N-phenyl phenolphthalein and 4,4'-difluorobenzophenone.
  • the polymer compositions can be miscible compositions, which have one or more of the following properties: no crystalline melting point, one glass transition temperature between 150 and 300 °C, or a modulus at 150-300 °C of greater than 1,000 MPa at 150-500 ⁇ m or 300 ⁇ m sample thickness measured according to ASTM D5418.
  • the miscible compositions comprise a poly(isoindolinones ether ether ketone) copolymer and a polyether ether ketone such as VICTREX PEEK available from Victrex Ltd., where the weight ratio of the poly(isoindolinones ether ether ketone) to the PEEK is 4:1 to 1:4 or 1:1 to 1:4.
  • the poly(isoindolinones ether ether ketone) copolymer can be derived from hydroquinone, N-phenyl phenolphthalein, and 4,4'-difluorobenzophenone.
  • the polymer compositions comprising the polyisoindolinones and the polyarylether ketones, including composites, can be used for the manufacture of a wide variety of articles.
  • the article can be in the form of a molded article, a layer (including a sheet or a film), one or more layers of a multilayer (which can contain sheets, films, or a combination thereof), an extruded article, a coating, a pellet, a powder, a foam, a tubing, a fiber, or a flake.
  • Such articles can be formed by a variety of methods, including molding (e.g., injection molding, blow molding, rotational molding, compression molding, transfer molding, and the like) thermoforming, casting, (e.g. spin-casting, vacuum casting, or dip casting, wax model casting,), pelletizing, coating, fiber spinning, extruding (including to form pellets or a profile), precipitating, 3D printing, and the like.
  • molding e.g., injection molding, blow molding, rotational molding, compression molding, transfer molding, and the like
  • thermoforming e.g., injection molding, blow molding, rotational molding, compression molding, transfer molding, and the like
  • casting e.g. spin-casting, vacuum casting, or dip casting, wax model casting,
  • pelletizing coating
  • fiber spinning including to form pellets or a profile
  • precipitating 3D printing
  • the articles can be used in a wide variety of applications, including electronic, medical, transportation, and construction.
  • articles include, but are not limited to, an optical lens, a site glass (also called a water gauge), optical fiber connector, an electrical connector, a light-emitting diode reflector, a printed circuit board substrate, a reflector for automotive headlamp, a component of a fuel system for a gasoline engine, or a diesel engine, an aircraft jet engine, or an aircraft turboprop engine, a fuel bowl, a fuel filter housing, water pump, a housing for a computer monitor, a housing or a handheld electronic device such as a cell phone or tablet computer, a component of a lighting fixture, or a component of a home appliance, industrial appliance, roof, greenhouse, sun rooms swimming pool enclosure, or the like, film, wire coatings, or the like.
  • the reaction content was then heated to 200°C, and maintained for 1 hour.
  • the temperature was then increased to 250°C, and maintained for 1 hour.
  • the temperature was raised to 325 °C, and maintained for 1 hour.
  • the light colored reaction mixture was then cooled (without end-stopping) and the resulting solid reaction product was milled into a fine powder.
  • the polymer product was purified by washing with acetone (3x), water (3x), and methanol (2x).
  • the resulting polymer powder was dried at 140° C under vacuum oven.
  • the polymer samples used for composition studies were dried, and premixed in a plastic bag with required quantities.
  • the polymer compositions were prepared by extrusion of dry powder mixtures of the polyether ether ketone, PEEK with polyisoindolinone ether-ketone (PIEEK) in a Haake Rheomix Lab Mixers from PolyLab using two roller blades. Compositions are listed in wt % of the total composition.
  • the Haake mixing bowl was set at 380-385 °C.
  • the compositions were run at 40-60 rpm under inert atmosphere of nitrogen.
  • the materials were mixed in the molten state for 5-15 min.
  • the resulting molten polymer mass was removed from Haake to obtain a polymer mass.
  • the polymer mass was then converted into smaller chunks/pellets using a grinder, and used for testing.
  • Films comprising the polymers or polymer compositions of the Examples were made by melt-pressing a polymer sample at a temperature above 350 °C using Automatic Bench Top Lab Press from Carver, Inc. Films were dried at 100 °C before testing.
  • DSC Differential scanning calorimetry
  • TGA Thermal gravimetric analysis
  • CTE coefficient of thermal expansion
  • TMA Thermal mechanical analysis
  • Modulus was determined according to ASTM D5418 on a 150-500 ⁇ m sample at the indicated temperatures.
  • Dynamic mechanical analysis was performed on a TA instrument 2980 DMA, and the scanning temperature range was from 40 °C to 400 °C at a heating rate of 2 °C /min and at a frequency of 1 Hz. It was run using the Tensile Fixture. A three-point bending mode was employed and the specimen size was 10.0-15.0 ⁇ 3.0-5.0 ⁇ 0.15-0.40 mm. The storage modulus (G'), loss modulus (G”) and tangent of loss angle (tan ⁇ ) were obtained as the function of scanning temperature.
  • DMA Dynamic mechanical analysis
  • the percent transmission of the polymer disc was measured using Perkin Elmer LAMBDA 950 across the 400 nm (UV) to 1600 nm (NIR) range.
  • the discs used for measurement had thickness of 150-500 ⁇ m as per ASTM D1003
  • PIEEK blends with PEEK are shown by the data in the Table 2, Examples 1-6, which compare the properties of PEEK versus the properties of compositions of polyisoindolinones and PEEK.
  • PIEEK/PEI blends and PIEEK/PPSU blends are shown by the data in Table 3, Examples 7-10, which compare the properties of the blends versus the properties of 100% PEI or 100% PPSU.
  • the formulations and the results are shown in Tables 2-5 as well as FIGS 1, 2 , and 3 .
  • Examples 1 and 2 show PEEK with 50 and 75 wt% of PIEEK-1 homopolymer.
  • Examples 3 and 4 are blends of the PIEEK-2 isoindolinone hydroquinone copolymer with PEEK.
  • Examples 5 and 6 are blends of PIEEK-3 isoindolinone hydroquinone copolymer with PEEK.
  • Comparative Example A is the unblended PEEK.
  • Table 2 PIEEK-PEEK Blends Component Example 1 Example 2 Example 3 Example 4
  • Example 5 Example 6 Comparative Example A PEEK (wt%) 50 25 50 25 50 25 100 PIEEK-1 (wt%) 50 75 - - - PIEEK-2 (wt%) - - 50 75 - PIEEK-3 (wt%) 50 75 - Tm (20 °C/min) 339 324 324 ND 337 330 341 Heat of fusion J/g 14.7 0.7 8.7 none 43.3 43.5 48.3 Tc (20 °C/min) 282 ND ND ND 282 264 301 Heat Crystallization J/g -18.1 none none none none none -47.4 -44.2 -50 Tg 1 (°C) by DSC 166 213 170 187
  • Tg glass transition temperature
  • Example 1 showed a crystallization temperature (Tc) above 282 °C, and crystalline melting point (Tm) of 338 °C
  • Example 5 showed a crystallization temperature (Tc) above 282 °C, and crystalline melting point (Tm) of 337 °C
  • Example 6 showed a crystallization temperature (Tc) above 264 °C, and crystalline melting point (Tm) of 330 °C whereas Examples 2-4 did not show any detectable Tc crystallization when cooled at 20 °C/min.
  • Example 3 did show slight crystalline melting point at 322 °C.
  • thermogravimetric analysis of Examples 1-6 and control showed an onset decomposition temperature of greater than 500 ° C, and % total weight loss under inert atmosphere of nitrogen between 47 and 55%.
  • the test demonstrated that examples 1-6 not only have good thermal stability but also good flame resistance, and the potential for high char formation.
  • melt-pressed films from examples 1-6 were found to be highly creasable. They had good creasability (HC) and did not crack or break after repeated (more than 7 times) flexing back on themselves.
  • Examples 1-6 had %T of more than 65% at 850 nm, 1310 nm, and 1550 nm as measured on an ultraviolet-visible/near infrared spectrophotometer , indicating that these compositions have good transparency.
  • the control example shows lower % transmission, in the range of 20-45%.
  • the blends showed substantially no blue phosphorescence in response to irradiation with ultraviolet light of 320-400 nm.
  • the films of the blends were insoluble in in dichloromethane, ortho-dichlorobenzene, or chloroform, showing less than 25 wt% loss at 23 °C after 24 hours, which is indicative of good chemical resistance, even in these aggressive chlorinated solvents.
  • Figure 1 shows the high temperature (130-240 °C) modulus of all the PIEEK compositions compared to PEEK with no polyisoindolinone.
  • Table 4 and Fig. 2 show the high temperature modulus of the PIEEK-1 homopolymer blends with PEEK. At 141-210 °C the blends show increase stiffness, higher flexural modulus, than the PEEK comparative example A. From 141-210 °C the PIEEK-1 blend modulus is above 400 MPa.
  • Table 4 High Temperature Modulus Data for PIEEK-PEEK Blends Temp (°C) Modulus (MPa) PEEK 50:50 PEEK-PIEEK-1 (Example 1) 25:75 PEEK-PIEEK-1 (Example 2) 145 1068 1570 1952 150 531 1505 1935 160 201 1145 1826 170 206 822 1533 180 204 684 1258 190 194 621 1010 200 187 562 745 210 181 448 454 220 175 240 110
  • Table 5 and Fig. 3 show the high temperature modulus of the PIEEK-2 hydroquinone copolymer blends with PEEK.
  • the blends show increased stiffness above 145 °C than the PEEK comparative example A.
  • At 150 °C modulus is above 1000 MPa for both blends.
  • Table 5 High Temperature Modulus Data for PIEEK-PEEK Blends Temp (°C) Modulus (MPa) PEEK 50:50 PEEK-PIEEK-2 (Example 3) 25:75 PEEK-PIEEK-2 (Example 4) 145 1068 1480 1897 150 531 1152 1865 160 201 84 1744 170 206 7 1041
  • the immiscible compositions of PIEEK and PEEK have a crystalline melting point of 300-350 °C as measured by differential scanning calorimetry per ASTM D3418 , two glass transitions between 150 and 300 °C as measured by differential scanning calorimetry per ASTM D3418 , and a modulus at 150-300 °C of greater than 300 MPa at 150-500 ⁇ m sample thickness measure according to ASTM D5418.
  • Tables 3 and 5 and FIG. 2 indicate that the miscible compositions of PIEEK and PEEK have no crystalline melting point, one glass transition temperature of 150-300 °C, and a modulus at 150-300 °C of greater than 1,000 MPa at 150-500 ⁇ m, or 300- ⁇ m sample thickness measured according to ASTM D5418.
  • Examples 7-10 showed only one Tg, indicating the formation of miscible compositions of PEI or PPSU with PEEK.
  • thermogravimetric analysis of Examples 7-10 showed an onset decomposition temperature of greater than 500 ° C, and % total weight loss under inert atmosphere of nitrogen between 57 and 67%.
  • melt-pressed films from examples 1-6 were found to be highly creasable. They had good creasability (HC) and did not crack or break after repeated (more than 7 times) flexing back on themselves.
  • Examples 7-10 had %T of more than 70% at 850 nm, 1310 nm, and 1550 nm as measured on an ultraviolet-visible/near infrared spectrophotometer , indicating that these compositions have good transparency.
  • hydrocarbyl and “hydrocarbon” refers broadly to a substituent comprising carbon and hydrogen, optionally with 1-3 heteroatoms, for example, oxygen, nitrogen, halogen, silicon, sulfur, or a combination thereof;
  • alkyl is a straight or branched chain, saturated monovalent hydrocarbon group;
  • alkylene is a straight or branched chain, saturated, divalent hydrocarbon group;
  • alkylidene is a straight or branched chain, saturated divalent hydrocarbon group, with both valences on a single common carbon atom;
  • alkenyl is a straight or branched chain monovalent hydrocarbon group having at least two carbons joined by a carbon-carbon double bond;
  • cycloalkyl is a non-aromatic monovalent monocyclic or multicylic hydrocarbon group having at least three carbon atoms;
  • cycloalkylene is a divalent group formed by the removal of two hydrogen atoms from two different carbon atoms on one or more rings
  • substituted means that at least one hydrogen on an atom or group is replaced with another group group or combination of groups, provided that the atom's normal valence is not exceeded, and that the substitution does not significantly adversely affect synthesis or use of the polymers.

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Claims (15)

  1. Eine Polymerzusammensetzung, die, basierend auf dem Gesamtgewicht der Polymere, Folgendes umfasst:
    1-99 Gewichtsprozent, vorzugsweise 10-90 Gewichtsprozent, einer Polymerkomponente, die ein Polyaryletherketon, ein Polybenzimidazol, ein Polyimid, ein Poly(arylethersulfon), ein Poly(phenylsulfid) oder eine Kombination umfasst, die mindestens eines der oben Genannten umfasst; und
    1-99 Gewichtsprozent, vorzugsweise 10-90 Gewichtsprozent, eines Polyisoindolinons, wobei das Polyisoindolinon Folgendes umfasst:
    1-100 Molprozent, vorzugsweise 5-100 Molprozent, von Isoindolinonetherketoneinheiten mit der Formel
    Figure imgb0039
     worin
    jedes R1 unabhängig gleich oder unterschiedlich ist und Wasserstoff, C1-8-Alkyl, C3-8-Cycloalkyl oder Phenyl, wahlweise substituiert mit 1-5 C1-6-Alkylgruppen, ist,
    jedes Ra unabhängig gleich oder unterschiedlich ist und C1-6-Alkyl ist,
    jedes Rb unabhängig gleich oder unterschiedlich ist und C1-12-Alkyl, C2-12-Alkenyl, C3-8-Cycloalkyl oder C1-12-Alkoxy ist,
    jedes Rc unabhängig gleich oder unterschiedlich ist und C1-12-Alkyl, C2-12-Alkenyl, C3-8-Cycloalkyl oder C1-12-Alkoxy ist,
    jedes p, q und r unabhängig gleich oder unterschiedlich ist und eine ganze Zahl von 0-4, vorzugsweise 0-2, ist und
    x eine ganze Zahl von 1-4, vorzugsweise 1-3, vorzugsweise 1 oder 2 ist; und
    0-99 Molprozent, vorzugsweise 0-95 Molprozent, von Arylenetherketoneinheiten mit der Formel
    Figure imgb0040
     worin
    jedes R2 unabhängig gleich oder unterschiedlich ist und ein substituiertes oder unsubstituiertes C6-30-Arylen ist,
    jedes Rc unabhängig gleich oder unterschiedlich ist und C1-12-Alkyl, C2-12-Alkenyl, C3-8-Cycloalkyl oder C1-12-Alkoxy ist,
    jedes r unabhängig gleich oder unterschiedlich ist und eine ganze Zahl von 0-4, vorzugsweise 0-2, ist und
    x eine ganze Zahl von 1-4, vorzugsweise 1-3, vorzugsweise 1 oder 2, ist; und
    worin das Polyisoindolinon, wenn es ein Poly(isoindolinonetheretherketon) ist, mindestens eine, vorzugsweise mindestens zwei, vorzugsweise alle der folgenden Eigenschaften hat:
    eine Glasübergangstemperatur von mehr als 150°C oder 150-270°C, bestimmt durch Differentialscanningkalorimetrie,
    weniger als 25 Gewichtsprozent Löslichkeit in Dichlormethan, Orthodichlorbenzol oder Chloroform bei 23°C oder
    im Wesentlichen keine blaue Phosphoreszenz als Reaktion auf Bestrahlung mit ultraviolettem Licht von 320-400 nm.
  2. Die Polymerzusammensetzung gemäß Anspruch 1, wobei die Zusammensetzung mindestens eines von Folgendem hat:
    eine Kristallinität von mindestens 10 Prozent, bestimmt durch Differentialscanningkalorimetrie, oder
    weniger als 20 Gewichtsprozent Löslichkeit bei 23°C in Dichlormethan, Dichlorethan oder Chloroform, wenn sie in Form einer schmelzgepressten Schicht vorliegt.
  3. Die Polymerzusammensetzung gemäß Anspruch 1 oder 2, die weiter mindestens eine oder alle der folgenden Eigenschaften hat:
    eine schmelzgepresste Schicht von 300 Mikrometern Dicke kann 180° größer als 3-mal gefaltet werden, ohne zu brechen; oder eine schmelzgepresste Schicht von 300 Mikrometern Dicke kann nach 3-tägigem Autoklavieren bei 130°C 180° mehr als 3-mal gefaltet werden, ohne zu brechen; oder
    einen Modul von mehr als 1000 MPa bei 150-300°C, gemessen nach ASTM D5418, an einer 300 Mikrometer dicken Schichtprobe.
  4. Die Polymerzusammensetzung gemäß einem oder mehreren der Ansprüche 1-3, wobei
    eine 300 Mikrometer dicke geformte Probe der Polymerzusammensetzung eine Durchlässigkeit von mindestens 70% bei 850 nm, 1310 nm oder 1550 nm hat, gemessen mit einem Spektrophotometer für den Ultraviolett-sichtbaren/nahen Infrarot-Bereich; oder
    eine 300 Mikrometer dicke geformte Probe der Polymerzusammensetzung mehr als 70% Durchlässigkeit hat, gemessen unter Verwendung des Farbraums CIE1931 (Leuchtmittel C und ein 2°-Beobachter).
  5. Die Polymerzusammensetzung gemäß einem oder mehreren der Ansprüche 1-4, wobei das Polyaryletherketon ein Poly(etheretherketon), ein Poly(etherketon), ein Poly(etherketonketon), ein Poly(ketonetherketonketon) oder eine Kombination ist, die mindestens eines der oben Genannten umfasst;
    wobei das Polyaryletherketon vorzugsweise eine Wiederholungseinheit mit den Formeln
    Figure imgb0041
    Figure imgb0042
    Figure imgb0043
    Figure imgb0044
     or
    Figure imgb0045
     oder eine Kombination umfasst, die mindestens eines der oben Genannten umfasst.
  6. Die Polymerzusammensetzung gemäß einem beliebigen oder mehreren der Ansprüche 1-5, wobei die Zusammensetzung Folgendes ist:
    eine nicht mischbare Zusammensetzung, die mindestens eine, vorzugsweise zwei, oder alle der folgenden Eigenschaften hat:
    einen Kristallschmelzpunkt von 300-350°C, gemessen durch Differentialscanningkalorimetrie nach ASTM D3418,
    zwei Glasübergänge zwischen 150 und 300°C, gemessen durch Differentialscanningkalorimetrie nach ASTM D3418, oder
    einen Modul, bei 150 bis 300°C, von mehr als 300 MPa bei einer Probendicke von 300 Mikrometern, gemessen nach ASTM D5418,
    wobei die Polymerzusammensetzung vorzugsweise 70-100 Molprozent der Isoindolinonetheretherketoneinheiten umfasst, basierend auf den Gesamtmol der Einheiten im Polyisoindolinon; oder
    eine mischbare Zusammensetzung, die mindestens eine, vorzugsweise zwei, oder alle der folgenden Eigenschaften hat:
    keinen Kristallschmelzpunkt, gemessen durch Differentialscanningkalorimetrie nach ASTM D3418;
    eine Glasübergangstemperatur zwischen 150 und 300°C, gemessen durch Differentialscanningkalorimetrie nach ASTM D3418; oder
    einen Modul, bei 150 bis 300°C, von mehr als 1.000 MPa bei einer Probendicke von 300 Mikrometern, gemessen nach ASTM D5418,
    wobei die Polymerzusammensetzung vorzugsweise 1-70 Molprozent der Isoindolinonetherketoneinheiten umfasst, basierend auf den Gesamtmol der Einheiten im Polyisoindolinon.
  7. Die Polymerzusammensetzung gemäß einem beliebigen oder mehreren der Ansprüche 1-6, wobei das Polyisoindolinon weiter mindestens eine, mindestens zwei, mindestens drei oder alle der folgenden Eigenschaften hat:
    weniger als 25 Teile je Million Teile nach Gewicht benzylische Protonen des Polyisoindolinons;
    einen Hydroxylpolymer-Endgruppengehalt von weniger als 700 Teilen je Million Teile nach Gewicht des Polyisoindolinons;
    einen Halogengehalt von weniger als 900 Teilen je Million Teile nach Gewicht des Polyisoindolinons;
    einen restlichen Erdalkalimetall-Kationengehalt von weniger als 500 Teilen je Million Teile nach Gewicht des Polyisoindolinons;
    einen restlichen Lösungsmittelgehalt von weniger als 500 Teilen je Million Teile nach Gewicht des Polyisoindolinons.
  8. Die Polymerzusammensetzung gemäß einem beliebigen oder mehreren der Ansprüche 1-7, wobei das Polyisoindolinon weiter mindestens eine, mindestens zwei, mindestens drei oder alle der folgenden Eigenschaften hat:
    ein Gewichtsmittel-Molekulargewicht von mindestens 15.000 Dalton, vorzugsweise 20.000-100.000 Dalton, stärker bevorzugt 20.000-60.000 Dalton, gemessen durch Gelpermeationschromatographie,
    eine Zersetzungsbeginntemperatur von mehr als 485°C, bestimmt durch thermogravimetrische Analyse in Stickstoff, einen Wärmeausdehnungkoeffizienten von 30-90 ppm/°C oder 30-60 ppm/°C oder 40-60 ppm/°C, bestimmt nach ASTM E831, mehr als 10% Kristallinität, bestimmt durch Differentialscanningkalorimetrie im zweiten Wärmezyklus, wobei Wärmen und Abkühlen mit einer Geschwindigkeit von 20°C/Minute, sowohl in den Wärme- als auch in den Kühlzyklen, stattfinden.
  9. Die Polymerzusammensetzung gemäß einem oder mehreren der Ansprüche 1-8, wobei das Polyisoindolinon folgende Eigenschaften hat:
    eine 300 Mikrometer dicke Schicht des Polyisoindolinons hat mindestens 70% Durchlässigkeit bei 850 nm, 1310 nm oder 1550 nm, gemessen mit einem Spektrophotometer für den Ultraviolett-sichtbaren/nahen Infrarotbereich; oder
    eine 300 Mikrometer dicke Schichtprobe hat mehr als 70% Durchlässigkeit, gemessen unter Verwendung des Farbraums CIE1931 (Leuchtmittel C und ein 2° Beobachter).
  10. Die Polymerzusammensetzung gemäß einem oder mehreren der Ansprüche 1-9, wobei das Polyisoindolinon weiter mindestens eine oder mindestens zwei der folgenden Eigenschaften hat:
    eine Wasseraufnahme von weniger als 3%, vorzugsweise weniger als 1%, am stärksten bevorzugt weniger als 0,6%, bei 23°C nach 24 Stunden direkten Eintauchens;
    eine Verschiebung der Schmelzviskosität von weniger als 30% über 30 min bei 380°C unter einer Stickstoffatmosphäre, gemessen mit einer Ablenkungsrheologie mit Oszillationszeit mit kleiner Amplitude bei einer festen Winkelfrequenz von 10 Radiant/Sekunde; oder
    einen Ertrag an künstlicher Kohle von mehr als 30 Gewichtsprozent, bestimmt durch thermogravimetrische Analyse unter einer inerten Stickstoffatmosphäre.
  11. Die Polymerzusammensetzungen gemäß einem beliebigen oder mehreren der Ansprüche 1-10, wobei das Polyisoindolinon bis zu 99 Molprozent, vorzugsweise 1-95 Molprozent, vorzugsweise 5-90 Molprozent, der Arylenetherketoneinheiten umfasst.
  12. Die Polymerzusammensetzung gemäß einem beliebigen oder mehreren der Ansprüche 1-11, wobei in dem Polyisoindolinon
    R2 ein substituiertes oder unsubstituiertes C6-30-Arylen mit folgender Formel ist:
    Figure imgb0046
     worin
    jedes Re unabhängig gleich oder unterschiedlich ist und C1-12-Alkyl, C2-6-Alkenyl, C3-6-Cycloalkyl oder C1-6-Alkoxy ist,
    jedes t unabhängig gleich oder unterschiedlich ist und eine ganze Zahl von 0-4 ist,
    jedes u unabhängig gleich oder unterschiedlich ist und eine ganze Zahl von 0-4 ist und
    Xa eine Einfachbindung, -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, -P(R) (=O)- ist, worin R ein C1-8-Alkyl oder C6-12-Aryl oder eine Brücken bildende organische C1-18-Gruppe ist;
    wobei R2 vorzugsweise abgeleitet ist von p-Hydrochinon, Methylhydrochinon, Dimethylhydrochinon, tert-Butylhydrochinon, di-tert-Butylhydrochinon, Resorcinol, 4,4'-Biphenol, 4,4'-Dihydroxydiphenylether, 4,4'-Isopropylidendiphenol, 4,4'-(Hexafluorisopropyliden)diphenol, bis(3,5-Dimethyl-4-hydroxyphenyl)isopropyliden, bis(4-Hydroxyphenyl)sulfoxid, bis(4-Hydroxyphenyl)sulfon, bis(4-Hydroxyphenyl)sulfid, bis(3,5-Dimethyl-4-hydroxyphenyl)sulfon, 4,4'-(1-Phenylethyliden)bisphenol, 4,4'-Dihydroxybenzophenon, 1,4-bis-(p-Hydroxybenzoyl)benzol, 1,3-bis(p-Hydroxybenzoyl)benzol oder einer Kombination, die mindestens eines der oben Genannten umfasst.
  13. Die Polymerzusammensetzung gemäß einem beliebigen oder mehreren der Ansprüche 1-12, worin
    R1 Wasserstoff, C1-6-Alkyl, C3-6-Cycloalkyl oder Phenyl, wahlweise substituiert mit 1-3 C1-6-Alkylgruppen, ist;
    Ra C1-4-Alkyl ist;
    jedes Rb unabhängig gleich oder unterschiedlich ist und C1-6-Alkyl, C2-6-Alkenyl, C3-6-Cycloalkyl oder C1-6-Alkoxy ist;
    jedes Rc unabhängig gleich oder unterschiedlich ist und C1-6-Alkyl, C2-6-Alkenyl, C3-8-Cycloalkyl oder C1-12-Alkoxy ist;
    jedes Rc unabhängig gleich oder unterschiedlich ist und C1-6-Alkyl, C2-6-Alkenyl, C3-6-Cycloalkyl oder C1-6-Alkoxy ist;
    jedes p, q, r und t unabhängig gleich oder unterschiedlich ist und eine ganze Zahl von 0 oder 1, vorzugsweise 0, ist;
    jedes u unabhängig gleich oder unterschiedlich ist und 0 oder 1 ist und
    jedes x unabhängig gleich oder unterschiedlich ist und eine ganze Zahl von 1-4, vorzugsweise 1-3, stärker bevorzugt 1 oder 2, ist.
  14. Ein Gegenstand, der die Polymerzusammensetzung gemäß einem beliebigen oder mehreren der Ansprüche 1-13 umfasst, wobei der Gegenstand vorzugsweise ein geformter Gegenstand, eine Schicht, eine oder mehrere Schichten eines mehrschichtigen Gegenstands, ein Extrudiererzeugnis, eine Beschichtung, ein Pellet, ein Pulver, ein Schaum, eine Rohrleitung, eine Faser oder eine Flocke ist;
    wobei der Gegenstand vorzugsweise eine optische Linse, ein Sichtglas, ein Glasfaserstecker, ein Stromstecker, ein LED-Reflektor, ein Leiterplattensubstrat, ein Reflektor für einen Fahrzeugscheinwerfer, eine Komponente eines Treibstoffsystems oder einer Wasserpumpe für einen Benzinmotor oder einen Dieselmotor, eine Flugzeugturbine oder ein Flugzeug-Turboprop-Triebwerk, ein Treibstoffbehälter oder ein Treibstofffiltergehäuse ist.
  15. Ein Verfahren zum Formen des Gegenstands gemäß Anspruch 14, welches das Formen, Extrudieren oder Spritzgießen der Polymerzusammensetzung gemäß einem beliebigen oder mehreren der Ansprüche 1-18 umfasst.
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WO2019053238A1 (en) * 2017-09-18 2019-03-21 Solvay Specialty Polymers Usa, Llc ADDITIVE MANUFACTURING METHOD FOR MANUFACTURING THREE-DIMENSIONAL OBJECT USING SELECTIVE LASER FRITTAGE

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US20190127575A1 (en) 2019-05-02
CN108884223A (zh) 2018-11-23
US10640645B2 (en) 2020-05-05
EP3443021A1 (de) 2019-02-20
WO2017180972A1 (en) 2017-10-19

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